CN110945080B - Dual-curable resin composition, cured body prepared therefrom, and electronic device comprising such cured body - Google Patents
Dual-curable resin composition, cured body prepared therefrom, and electronic device comprising such cured body Download PDFInfo
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Abstract
The present invention provides a dual curable resin composition comprising: (A) A first polyorganosiloxane containing at least one alkenyl group and at least one alkoxy group in one molecule; (B) A second polyorganosiloxane containing at least two photoreactive functional groups in one molecule on a side chain of the siloxane main chain; (C) At least one silane compound represented by a specific chemical formula or a partially hydrolyzed compound thereof; (D) at least one photoinitiator; (E) at least one condensation reaction catalyst. Further, a cured body prepared by curing the dual curable resin composition and an electronic device including the cured body are provided.
Description
Cross Reference to Related Applications
This application claims priority and all advantages of korean patent application No.10-2017-0097097, filed on 31/7/2017, the contents of which are incorporated herein by reference.
Technical Field
Disclosed are a dual-curable resin composition, a cured body prepared therefrom, and an electronic device comprising the cured body.
Background
Silicone materials are widely used not only in the consumer market, but also in industry for sealants, adhesives, coatings, potting compounds, and the like. Such materials include Room Temperature Vulcanizing (RTV) silicones, high Temperature Vulcanizing (HTV) silicones, and photo-curable (UV-Vis) silicones, among others, which can be cured by moisture in air at room temperature.
Generally, room temperature curable silicone materials (or moisture curable silicone materials) are used as sealants and adhesives in electronic devices because a separate heating process is not required for curing. This room-temperature-curable silicone composition has the following characteristics: if it is in a cured state when it contacts the circuit or the electrode, the silicone cured body can be removed from the circuit or the electrode even after a long period of time, and can be repaired and recovered.
However, the room-temperature curable silicone composition has a disadvantage in that it takes a long time to completely cure. Also, in the case of a general room temperature curable silicone composition, since its adhesion to a substrate is good, there is a problem that the cured body is broken or cohesive failure is caused when the silicone cured body is removed from an organic substrate.
Unlike room temperature curable silicone compositions, photocurable silicone compositions exhibit very high reaction rates due to free radical polymerization by UV-Vis light. Due to the fast curing rate of such photocurable silicone materials, cured bodies can be provided very quickly.
However, the photocurable silicone composition has excellent curability in a surface region in direct contact with UV-Vis irradiation, but has poor curability in a masked region, and particularly, there is a problem that a material in the region is not irradiated with UV-visible light and cannot be cured.
It would be desirable to find a dual curable composition that exhibits excellent properties for both room temperature curing and curing by UV-Vis radiation, without exhibiting the disadvantages of known curable silicone materials as described above.
Documents of the prior art
Patent document 1: patent publication WO 2015/098118 (2015.07.02)
Disclosure of Invention
Technical problem
One embodiment provides a dual curable resin composition which can be rapidly cured by light and high hardness and has excellent curability, excellent adhesion and releasability in a masked region.
Another embodiment provides a cured body prepared by curing the dual curable resin composition.
Another embodiment provides an electronic device including a cured body.
Solution to the problem
According to one embodiment, there is provided a dual curable resin composition comprising: (A) A first polyorganosiloxane containing in one molecule at least one alkenyl group and at least one alkoxy group; (B) A second polyorganosiloxane containing at least two photoreactive functional groups in one molecule on a side chain of the siloxane main chain; (C) At least one silane compound represented by the following chemical formula 1 or a partially hydrolyzed compound thereof; (D) at least one photoinitiator; (E) at least one condensation reaction catalyst:
(R x ) 2 SiX 2 [ chemical formula 1]
Wherein, in chemical formula 1, R X Is a monovalent hydrocarbon group, and X is a C1 to C20 alkoxy group, a hydroxyl group, a halogen, a carboxyl group, or a combination thereof.
The first polyorganosiloxane may be represented by the following chemical formula 2.
Wherein, in chemical formula 2, R 1 To R 8 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof; however,
R 1 to R 6 Is a substituted or unsubstituted C2 to C20 alkenyl group, and
R 1 to R 6 Is a substituted or unsubstituted C1 to C20 alkoxy group,
n is an integer in the range of 50 to 1000.
The photoreactive functional group may be a thiol group.
In chemical formula 2, R 1 To R 6 May be a substituted or unsubstituted C2 to C10 alkenyl group, and R 1 To R 6 Is a substituted or unsubstituted C1 to C10 alkoxy group.
A second polyorganosiloxane represented by the following chemical formula 3:
wherein, in chemical formula 3,
R 9 to R 14 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof;
R 15 to R 18 Each independently is a mercapto group, a monovalent hydrocarbon group comprising a mercapto group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a combination thereof; however,
R 17 and R 18 At least one of which is a mercapto group or a monovalent hydrocarbon group containing a mercapto group, and
p is an integer ranging from 0 to 100, and q is an integer ranging from 2 to 100.
In chemical formula 3, R 15 And R 16 May each independently be a substituted or unsubstituted C1 to C20 alkyl group, R 17 Or R 18 May be a monovalent hydrocarbon group containing a mercapto group, p may be an integer in the range of 0 to 100, and q may be an integer in the range of 2 to 100.
In chemical formula 3, R 9 To R 14 May each independently be a substituted or unsubstituted C1 to C10 alkaneAnd (4) a base.
In chemical formula 1, R X May be a substituted or unsubstituted C1 to C4 alkyl group, and X is a C1 to C6 alkoxy group.
The photoinitiator (D) may comprise at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate.
The condensation reaction catalyst (E) may comprise at least one of tetrakis (isopropoxy) titanium, tetrakis (n-butoxy) titanium, tetrakis (t-butoxy) titanium, bis (isopropoxy) bis (ethylacetate) titanium, bis (isopropoxy) bis (methylacetoacetate) titanium, and bis (isopropoxy) bis (acetylacetonato) titanium.
The dual curable resin composition may include 1 to 30 parts by weight of (B) a second polyorganosiloxane, 0.5 to 30 parts by weight of (C) a silane compound or a partially hydrolyzed compound thereof, 0.05 to 5 parts by weight of (D) a photoinitiator, and 0.01 to 10 parts by weight of (E) a condensation reaction catalyst, relative to 100 parts by weight of (a) a first polyorganosiloxane.
The dual curable resin composition may further include (F) an additive including at least one of a reinforcing filler, a photopolymerization inhibitor, and a pigment.
According to another embodiment, a cured body prepared by curing a dual curable resin composition is provided.
According to another embodiment, an electronic device including a cured body is provided.
Effects of the invention
The dual curable resin composition according to an embodiment can be rapidly cured by light and has excellent curability in a masked region.
In addition, the cured body prepared by curing the dual curable composition according to one embodiment exhibits high hardness and has excellent adhesion and releasability, and thus excellent repairability and reworkability when used in an electronic device.
Detailed Description
Hereinafter, exemplary embodiments of the present invention will be described in detail. The exemplary embodiments are intended as illustrations, which are embodied to describe the invention, and are not intended to limit the scope of the invention.
As used herein, the term "monovalent hydrocarbon group" when a specific definition is not otherwise provided may refer to an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or a halogenated alkyl group.
As used herein, when a specific definition is not otherwise provided, the term "alkyl" may refer to a C1 to C20 alkyl group, the term "cycloalkyl" may refer to a C3 to C20 cycloalkyl group, the term "alkenyl" may refer to a C2 to C20 alkenyl group, the term "aryl" may refer to a C6 to C20 aryl group, the term "aralkyl" may refer to a C6 to C20 aralkyl group, and the term "haloalkyl" may refer to a C1 to C20 alkyl group, wherein at least one hydrogen of the alkyl group is substituted with at least one of the halogens.
As used herein, the term "substituted" when a specific definition is not otherwise provided may refer to a substituent substituted with at least one substituent comprising: halogen (F, br, cl, or I), hydroxyl, C1 to C20 alkoxy, nitro, cyano, amino, azido, amidino, hydrazine, hydrazono, carbonyl, carbamate, mercapto (thiol), ester, ether, carboxyl or salt thereof, sulfonic acid or salt thereof, phosphoric acid or salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl, or combinations thereof, in place of the hydrogen of the compound.
As used herein, the term "hetero", when a specific definition is not otherwise provided, may refer to at least one heteroatom selected from N, O, S and P in one chemical formula.
As used herein, the term "combination" when a specific definition is not otherwise provided means mixing or copolymerization.
Hereinafter, a dual curable resin composition according to an embodiment is described.
According to one embodiment, there is provided a dual curable resin composition comprising: (A) A first polyorganosiloxane containing at least one alkenyl group and at least one alkoxy group in one molecule; (B) A second polyorganosiloxane containing at least two photoreactive functional groups in one molecule on a side chain of the siloxane main chain; (C) At least one silane compound represented by the following chemical formula 1 or a partially hydrolyzed compound thereof; (D) at least one photoinitiator; (E) at least one condensation reaction catalyst:
(R x ) 2 SiX 2 [ chemical formula 1]
Wherein, in chemical formula 1, R X Is a monovalent hydrocarbon group, and X is a C1 to C20 alkoxy group, a hydroxyl group, a halogen, a carboxyl group, or a combination thereof.
Conventional photocurable silicone compositions are suitable for fast curing processes, but have good curability only in the surface region in direct contact with UV radiation and poor curability in the masked region, resulting in lack of cure progression in that region. In addition, the moisture-curable resin composition has a problem of slow curing speed, and thus its curing speed is not suitable for rapidly supporting an automated manufacturing process.
The dual curable resin composition according to an embodiment includes: a first polyorganosiloxane, a second polyorganosiloxane, a silane compound represented by chemical formula 1, or a partially hydrolyzed compound thereof; accordingly, an embodiment provides a dual curable resin composition that can be rapidly cured by light and high hardness and has excellent curability, excellent adhesion, and releasability in a masked region.
In particular, a first polyorganosiloxane containing at least one alkenyl group and at least one alkoxy group in one molecule is condensed with a second polyorganosiloxane containing at least two photoreactive functional groups in one molecule on its side chain. As a result, a rapid initial curing speed can be ensured. Therefore, it is suitable for improving the efficiency of the manufacturing schedule. In addition, the dual curable resin composition including the silane compound represented by chemical formula 1 according to one embodiment shows excellent hardness by being cured in the uncured mask region after photo-curing. In addition, a cured body prepared by using the dual curable resin composition according to an embodiment exhibits excellent adhesion to a substrate and peelability; therefore, an electronic device using such a cured body exhibits excellent repairability and reworkability.
Hereinafter, each component of the dual curable resin composition according to the embodiment is described in detail.
(A) A first polyorganosiloxane
The first polyorganosiloxane (a) according to an embodiment includes at least one alkenyl group and at least one alkoxy group in one molecule.
In one embodiment, the first polyorganosiloxane may include at least one alkenyl group and at least two alkoxy groups in one molecule.
The first polyorganosiloxane according to one example may be represented by the following chemical formula 2.
Wherein, in chemical formula 2,
R 1 to R 8 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof; however,
R 1 to R 6 Is a substituted or unsubstituted C2 to C20 alkenyl group, and
R 1 to R 6 Is a substituted or unsubstituted C1 to C20 alkoxy group,
n is an integer in the range of 50 to 1000.
In one implementation, R 1 To R 6 At least one of which may be a substituted or unsubstituted C2 to C12 alkenyl group, for example, may be a substituted or unsubstituted C2 to C4 alkenyl group, for example, may be a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, or dodecenyl group.
In one embodiment, R 1 To R 6 At least one of which may be a substituted or unsubstituted C1 to C10 alkoxy group, for example, may be a C1 to C4 alkoxy group, for example, may be a methoxy, ethoxy, propoxy or butoxy group.
In one implementation, R of chemical formula 2 1 To R 6 At least two of (a) may be a substituted or unsubstituted C1 to C20 alkoxy group, for example, may be a substituted or unsubstituted C1 to C10 alkoxy group, for example, may be a substituted or unsubstituted C1 to C4 alkoxy group.
In one implementation, the first polyorganosiloxane may have a weight average molecular weight of 20,000 to 50,000. In addition, the viscosity of the first polyorganosiloxane according to an embodiment may be 400cst to 3,000cst. When the viscosity of the first polyorganosiloxane is within the above range, the workability and processability of the resulting dual-curable resin composition are improved, and the mechanical strength of the cured body according to an embodiment is improved.
(B) Second polyorganosiloxanes
The second polyorganosiloxane according to an embodiment includes at least two photoreactive functional groups in one molecule. The photoreactive functional group in the second polyorganosiloxane is pendant to its siloxane backbone and forms a crosslink with the first polyorganosiloxane.
The photoreactive functional group means that photoreactivity can be exhibited when irradiated with light (UV/Vis). Specifically, when light is irradiated, the photoreactive functional group causes photoreaction, in which process the photoreactive functional group located on the main chain and/or side chain of the siloxane main chain forms a radical by a photoinitiator. Thus, a polycondensation reaction occurs.
In one example, the photoreactive functional group is located on a side chain of the main chain of the second polyorganosiloxane, thereby exhibiting an increase in crosslinking density because the photoreactive functional group is combined with functional groups, i.e., alkenyl groups, located at both ends of the first polyorganosiloxane. In addition, it exhibits superior hardness, elasticity and strength after curing, as compared to a combination with a photoreactive functional group located at the end of a siloxane main chain.
In one implementation, the photoreactive functional group may be a mercapto group (-SH), for example, when light is irradiated, the mercapto group forms a thienyl group (-S · to cause crosslinking with an alkenyl group contained in the first polyorganosiloxane.
By such radical crosslinking, a fast-curing dual-curable resin composition can be provided. As is well known in the art, many moisture-curable silicone materials provide excellent physical properties and performance when fully cured, but have the disadvantage of slow curing. However, the second polyorganosiloxane according to one embodiment solves the disadvantages of the moisture-curable resin composition due to the inclusion of the photoreactive functional group in the molecule.
The second polyorganosiloxane according to one example may be represented by the following chemical formula 3.
Wherein, in chemical formula 3,
R 9 to R 14 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof;
R 15 to R 18 Each independently is a mercapto group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C6 to C20 aralkyl, substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C1 to C20 heterocycloalkyl, substituted or unsubstituted C1 to C20 heteroaryl, or combinations thereof; however,
R 17 and R 18 At least one of which is a mercapto group or a monovalent hydrocarbon group containing a mercapto group, and
p is an integer ranging from 0 to 100, and q is an integer ranging from 2 to 100.
In one implementation, R 17 And R 18 May be a mercapto group (-SH) or a substituted or unsubstituted C1 to C20 alkyl group containing a mercapto group.
In one implementation, R 17 And R 18 At least one of (a) may be a substituted or unsubstituted mercapto group-containing C1 to C20 alkyl group, for example, a substituted or unsubstituted mercapto group-containing C1 to C10 alkyl group, for example, a substituted or unsubstituted mercapto group-containing C1 to C4 alkyl group.
In one implementation, R 15 And R 16 May each independently be a substituted or unsubstituted C1 to C20 alkyl group, R 17 Or R 18 May be a monovalent hydrocarbon group containing a mercapto group, wherein p may be an integer ranging from 0 to 100, and q may be an integer ranging from 2 to 100.
In one implementation, R 9 To R 14 May each independently be a substituted or unsubstituted C1 to C20 alkyl group, for example may be a C1 to C10 alkyl group, for example may be a C1 to C4 alkyl group.
In one implementation, R 9 To R 14 Each independently may be methyl, ethyl, propyl or butyl.
In one implementation, the first polyorganosiloxane can have a weight average molecular weight of 500 to 1,500. In addition, the second polyorganosiloxane according to an embodiment has a viscosity of 50cst to 250cst. When the viscosity of the second polyorganosiloxane is within the above range, the workability and processability of the resulting dual curable resin composition are improved.
The second polyorganosiloxane may comprise 1 to 30 parts by weight, such as 1 to 20 parts by weight, such as 5 to 15 parts by weight, relative to 100 parts by weight of the first polyorganosiloxane. When the second polyorganosiloxane is in the above range, a rapid initial curing rate can be ensured, and excellent storage stability is exhibited.
(C) Silane compounds or partially hydrolyzed compounds thereof
The dual curable resin composition according to an embodiment includes (C) at least one of a silane compound represented by the following chemical formula 1 or a partially hydrolyzed compound thereof. The silane compound represented by chemical formula 1 forms a crosslink with the first polyorganosiloxane.
(R x ) 2 SiX 2 [ chemical formula 1]
Wherein, in chemical formula 1,
R X is a monovalent hydrocarbon group, and X is a C1 to C20 alkoxy group, a hydroxyl group, a halogen, a carboxyl group, or a combination thereof.
The dual curable resin composition according to an embodiment may include at least two or more compounds represented by chemical formula 1.
In one implementation, R x And may be a substituted or unsubstituted C1 to C4 alkyl group, such as methyl, ethyl, propyl, or butyl.
In one implementation, X may be a C1 to C6 alkoxy group, such as methoxy or ethoxy.
In one implementation, the silane compound represented by chemical formula 1 may be dimethyldimethoxysilane or dimethyldiethoxysilane, but is not limited thereto.
The silane compound represented by chemical formula 1 or a partially hydrolyzed compound thereof may include 0.5 to 30 parts by weight, for example, 0.5 to 20 parts by weight, for example, 0.5 to 15 parts by weight, with respect to 100 parts by weight of the first polyorganosiloxane. When the silane compound is contained within the above range, curability of the dual curable resin composition according to an embodiment may be sufficiently ensured, and at the same time, the shelf life of the resulting composition under moisture resistance is improved, and the resulting composition may be rapidly cured by moisture in the air.
(D) Photoinitiator
The dual curable resin composition according to one embodiment includes at least one photoinitiator. The photoinitiator induces a light curing reaction, and conventionally a known photoinitiator that can be generally used in a photocurable resin composition can be used.
The photoinitiator according to one embodiment is not limited to the photoinitiator and the photoinitiator co-agent as long as it absorbs light in ultraviolet light or visible light and is capable of radical polymerization. For example, the photoinitiator may be one or a mixture of two or more selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethyl phenylphosphinate, and the like.
In one implementation, the photoinitiator may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, or ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, for example may be bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
The photoinitiator may comprise 0.05 to 5 parts by weight, for example 0.05 to 2 parts by weight, for example 0.05 to 1 part by weight, relative to 100 parts by weight of the first polyorganosiloxane. When the photoinitiator is included in the above range in the dual curable resin composition according to the example, photopolymerization may be sufficiently performed at the time of exposure. Therefore, photopolymerization occurs sufficiently at the time of irradiation, and rapid curing can be performed without being affected by an unreacted initiator, and a cured body exhibiting sufficient hardness can be obtained.
(E) Condensation reaction catalyst
The dual curable resin composition according to one embodiment includes at least one condensation reaction catalyst. The condensation reaction catalyst (E) according to one embodiment may be a titanium compound.
For example, the condensation reaction catalyst may be tetrakis (isopropoxy) titanium, tetrakis (n-butoxy) titanium, tetrakis (t-butoxy) titanium, bis (isopropoxy) bis (ethylacetoacetate) titanium, bis (isopropoxy) bis (methylacetoacetate) titanium or bis (isopropoxy) bis (acetylacetonato) titanium, but is not limited thereto.
In one embodiment, the condensation reaction catalyst may be titanium bis (isopropoxide) bis (ethylacetoacetate).
The condensation reaction catalyst may comprise 0.01 to 10 parts by weight, for example 0.05 to 5 parts by weight, for example 0.05 to 3 parts by weight, relative to 100 parts by weight of the first polyorganosiloxane. When the condensation reaction catalyst within the above range is included in the dual curable resin composition according to an exemplary embodiment, the resultant composition may rapidly react, thereby being rapidly cured by moisture in the air.
(F) Additive agent
The dual curable resin composition according to an embodiment may further include at least one additive. The additive (F) according to one embodiment may be a reinforcing filler, a photopolymerization inhibitor, a pigment, and a mixture thereof.
The reinforcing filler may include, for example, fumed silica fine powder, precipitated silica fine powder, fused silica fine powder, baked silica fine powder, fumed titanium oxide fine powder, glass fiber, and hydrophobized fine powder obtained by surface-treating these fine powders with organosilanes, silazanes, and siloxane oligomers, and may be, for example, fumed silica fine powder. The particle diameter of the fine powder is not particularly limited, but the median particle diameter by a measurement method using a laser diffraction/scattering type particle diameter distribution may be, for example, in the range of 0.01 μm to 1,000 μm.
The reinforcing filler may comprise 0.1 to 50 parts by weight, such as 1 to 50 parts by weight, such as 10 to 30 parts by weight, relative to 100 parts by weight of the first polyorganosiloxane.
According to one embodiment, the photopolymerization inhibitor inhibits radical reaction during photocuring of the dual-curable resin composition. In one implementation, the photopolymerization inhibitor includes hydroquinone, t-butyl hydroquinone, p-methoxyphenol, nitrobenzophenone, BHT (2,6-di-tetrabutyl-4-methylphenol), N-nitrosophenylhydroxylamine aluminum, and the like.
In one implementation, the photopolymerization inhibitor may be dibutylhydroxytoluene or a combination of dibutylhydroxytoluene and N-nitrosophenylhydroxyaluminum.
The photopolymerization inhibitor may be contained in an amount of 0.01 to 1 part by weight, for example, 0.01 to 0.5 part by weight, for example, 0.01 to 0.1 part by weight, relative to 100 parts by weight of the first polyorganosiloxane.
The pigment is used for visual distinction in the application of the dual curable resin composition, and may be used as a material having a color expression and being transmittable by light (UV-Vis), but is not limited thereto. In one implementation, the pigment is used in small amounts and may comprise sodium aluminosilicate or iron oxide or the like.
In addition, the dual curable resin composition may have added thereto an amount of other additives such as an antioxidant, an ultraviolet absorber, a plasticizer, an adhesion promoter, a filler, a photosensitizer, a surfactant, and the like, within a range that does not impair physical properties.
According to another embodiment, a cured body prepared by using the dual curable resin composition is provided.
The cured body is prepared by curing the dual curable resin composition according to one embodiment. The curing method is not particularly limited, but in one example, first, a photocuring reaction is performed by exposure to light (UV-Vis) to perform rapid curing, and then the composition is further cured by contact with moisture in the air, thus preparing a cured body according to an embodiment by curing the UV-Vis exposed portion and the masked region.
The cured body according to one embodiment exhibits excellent adhesion to a substrate in contact during curing, and exhibits good releasability since it can be effectively peeled from the substrate.
According to yet another embodiment, an electrical and electronic device including a cured body is provided.
The electric and electronic devices are not particularly limited, but examples thereof include electronic devices including a circuit or an electrode in which a metal oxide film electrode such as Indium Tin Oxide (ITO) is formed, and a metal electrode made of silver, copper, aluminum, gold, or the like on a substrate such as glass, epoxy resin, polyimide resin, phenol resin, ceramic, or the like. Examples of such electrodes include electrodes of Liquid Crystal Display (LCD) devices, various PCB modules, and the composition of the present invention can be used for coating and sealing of electrodes, water tightness of various electrical and electronic devices, protective potting for air tightness, gap filling, etc. with rapid curing properties, excellent repairability and reworkability.
In one implementation, such electronic devices can be repaired and reworked due to high adhesion to and high release from the contacted substrate during curing of the cured body.
In particular, the dual curable resin composition according to one embodiment may be used as a gap filling composition for electronic or semiconductor articles. The dual curable resin composition maintains good fluidity, thereby easily filling narrow gaps between the articles. Therefore, the cured body prepared by UV-vis irradiation sufficiently fills a narrow gap for electronic or semiconductor products to tightly seal the gap against water, airtightness, and reliability thereof. Further, if desired, the cured body can be easily removed without any residue, and good reworkability can be provided for an article having the cured body from the dual-curable resin composition.
It is to be understood that the appended claims are not limited to the specific and specific compounds, compositions, or methods described in the detailed description, as these may vary between specific embodiments within the scope of the appended claims. For any markush group relied upon herein to describe a particular feature or aspect of various embodiments, different, special and/or unexpected results may be obtained from each member of the respective markush group independently of all other markush members. Each member of the markush group may be relied upon individually and/or in combination and provide adequate support for specific embodiments within the scope of the appended claims.
Moreover, any ranges and subranges relied upon in describing the various embodiments of the invention are independently and collectively within the scope of the appended claims, and it is understood that all ranges including all and/or some values therein are described and contemplated, even if such values are not explicitly written herein. Those skilled in the art will readily recognize that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As but one example, a range of "from 0.1 to 0.9" may be further delineated into a lower third (i.e., from 0.1 to 0.3), a middle third (i.e., from 0.4 to 0.6), and an upper third (i.e., from 0.7 to 0.9), which are individually and collectively within the scope of the appended claims, and which may be relied upon individually and/or collectively and provide sufficient support for specific embodiments within the scope of the appended claims. Further, with respect to language such as "at least," "greater than," "less than," "no more than," and the like, defining or modifying a range, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes at least a sub-range of 10 to 35, at least a sub-range of 10 to 25, a sub-range of 25 to 35, and the like, and each sub-range may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. Finally, independent numerical values within the disclosed ranges may be relied upon and provide sufficient support for specific embodiments within the scope of the appended claims. For example, a range of "from 1 to 9" includes individual integers such as 3, and individual numbers including decimal points (or fractions) such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
Hereinafter, the following examples illustrate the present invention in more detail. However, it should be understood that the present invention is not limited to these examples.
Examples
Synthesis example 1: synthesis of first polyorganosiloxane (A-1)
100 parts by weight of hydroxyl-terminated Polydimethylsiloxane (PDMS) and 5 to 10 parts by weight of vinyltrimethoxysilane were added to a 500ml three-necked flask with 0.03 to 0.1 part by weight of acetic acid, and the mixture was mixed with a stirrer, and then the temperature was raised to a temperature of about 150 ℃ to about 160 ℃ with stirring. After 3 hours, the reaction mixture was vacuum cracked to remove residual catalyst and vinyltrimethoxysilane.
Examples 1 to 2 and comparative examples 1 to 5: preparation of Dual-curable resin composition
The second polyorganosiloxane, the silane compound, and the first polyorganosiloxane prepared in synthesis example 1, and the following components were mixed in the composition shown in table 1, and then stirred at room temperature. Thus, dual curable resin compositions were prepared according to examples 1 to 2 and comparative examples 1 to 5.
(B-1) a second polyorganosiloxane: the [ (mercaptopropyl) methylsiloxane ] -dimethylsiloxane copolymer represented by the following chemical formula a has trimethylsiloxy groups at both terminals:
wherein m is 43 and n is 5.
(B-2) a mercaptodimethoxy-terminated polydimethylsiloxane represented by the following chemical formula B:
where n is a number that provides a viscosity of 450cst (at 25 ℃).
(D) Photoinitiator (2): (2,4,6-trimethylbenzoyl) phenylphosphinic acid ethyl ester
(E) Condensation reaction catalyst: diisopropoxybis (ethyl acetoacetate) titanium
(F-1) reinforcing filler: fumed silica
(F-2) photopolymerization inhibitor: dibutylhydroxytoluene
(F-3) pigment: sodium aluminosulfosilicate
TABLE 1
(unit: parts by weight)
Preparation of cured body and evaluation thereof
The dual curable resin compositions prepared according to examples 1 to 2 and comparative examples 1 to 5 were exposed to 1,000mJ/cm by photo-curing using UV LED lamps irradiated at 395nm or 405nm wavelength 2 To 5,000mJ/cm 2 And a photo-curing reaction is performed. Then, room temperature curing was performed at 25 ℃. + -. 2 ℃ and a relative humidity of 50%. + -. 5%, thereby preparing a cured body.
(1) Adhesion test and cohesive failure
An adhesive layer comprising the resin composition according to examples 1 to 2 and comparative examples 1 to 5 was coated on a glass substrate so that the size thereof was 25mm × 10mm × 1mm, and another glass substrate was coated thereon to prepare a form capable of being subjected to a shear test.
Samples were prepared by the following methods, respectively: 1) curing by light (UV-Vis) exposure, 2) further curing the light-cured sample by curing at Room temperature under conditions of 25 ℃ ± 2 ℃ and 50% ± 5% Room Humidity (RH) for 7 days, 3) curing only at Room temperature under conditions of 25 ℃ ± 2 ℃ and 50% ± 5% Room Humidity (RH) for 7 days without light (UV-Vis) exposure.
Lap shear adhesion testing was performed by using a tensile tester to pull the cured sample continuously up and down at a speed of 50 mm/min. After the lap shear adhesion test, the state of the adhesive fracture surface was visually observed, and the proportion of the dual-curable resin composition causing cohesive failure was taken as a cohesive failure (hereinafter CF) ratio.
A CF ratio of 100% means that after testing, a film of the cured adhesive remains about 100% on the substrate, indicating poor release.
A CF ratio of 50% means that a film of the cured adhesive remains about 50% on the substrate after testing.
The CF ratio of 0% means that cohesive failure during peeling of the silicone rubber cured product is suppressed, and the silicone rubber cured product has good releasability from the substrate.
(2) Hardness of
The resin compositions according to examples 1 to 2 and comparative examples 1 to 5 were prepared by preparing a sheet-like sample having a thickness of 1mm to 2mm and photocuring the sample. Then, the hardness was evaluated by further curing at Room temperature under the conditions of 25 ℃ ± 2 ℃ and 50% ± 5% Room Humidity (rom Humidity, RH) for 7 days, and then laminating it to a thickness of 6nm to 8nm, and then the shore hardness of each cured body was measured.
Shore A hardness was measured using ASTM D2240-05.
TABLE 2
The cured bodies of examples 1 to 2 included: the cured body maintains excellent hardness of shore a 30 or more and does not suffer from cohesive failure after photocuring and/or moisture curing, and thus exhibits excellent releasability, as shown in table 2, (a) a first polyorganosiloxane containing at least one alkenyl group and at least one alkoxy group in one molecule, (B) a second polyorganosiloxane containing at least two photoreactive functional groups in one molecule on a side chain of a siloxane main chain, and (C) at least one silane compound represented by the following chemical formula 1 or a partially hydrolyzed compound thereof.
On the other hand, in comparative example 2 containing only a silane compound as a room temperature curing resin, there was a problem that photocuring was not caused and the curing reaction speed was considerably slow. In addition, comparative example 3 containing vinyl terminated polydimethylsiloxane did not show curing in the masked region since it did not contain a silane compound necessary for room temperature curing. In addition, comparative example 4, which includes an organic curing agent having three mercapto groups, shows a rapid curing property by a light (UV-Vis) reaction, and can be cured in a shadow region upon exposure. However, since miscibility with the first polyorganosiloxane is poor, transparency is reduced during mixing, separation during storage is caused, and adhesion to a substrate after curing is reduced.
Unlike the second polyorganosiloxane according to an embodiment, comparative example 5 (in which a mercapto group in a molecule is located at a terminal of a siloxane main chain) first reacts with a functional group at a terminal of the first polyorganosiloxane when cured by UV-Vis exposure; therefore, the reaction to increase the length of the resin is prioritized over the crosslinking reaction. Therefore, the cured density of the cured composition was significantly reduced, and the cured body showed 100% cohesive failure rate in terms of adhesion to the substrate after photocuring and room temperature curing.
In addition, according to comparative example 1 including a silane compound other than the silane compound of formula 1 according to one embodiment, the cohesive failure rate of adhesion to a substrate after moisture curing is 100%.
Therefore, the dual curable resin composition according to one embodiment has excellent adhesion and peelability after photo-curing and/or moisture-curing, and the cured body prepared therefrom exhibits excellent hardness. In addition, an electronic device including such a cured body exhibits excellent repairability and reworkability.
Many modifications and other embodiments of the invention will come to mind to one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims.
Claims (13)
1. A dual curable resin composition comprising:
(A) 100 parts by weight of a first polyorganosiloxane containing in one molecule at least one alkenyl group and at least one alkoxy group;
(B) 1 to 30 parts by weight of a second polyorganosiloxane containing at least two photoreactive functional groups in one molecule on a side chain of a siloxane main chain;
(C) 0.5 to 30 parts by weight of at least one silane compound represented by the following chemical formula 1 or a partially hydrolyzed compound thereof;
(R x ) 2 SiX 2 [ chemical formula 1]
Wherein, in chemical formula 1, R X Is a monovalent hydrocarbon group, X is a C1 to C20 alkoxy group, a hydroxyl group, a halogen, a carboxyl group, or a combination thereof;
(D) 0.05 to 5 parts by weight of at least one photoinitiator; and
(E) 0.01 to 10 parts by weight of at least one condensation reaction catalyst;
wherein the (B) second polyorganosiloxane is represented by the following chemical formula 3:
wherein, in chemical formula 3,
R 9 to R 14 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 hetero ringAn alkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof;
R 15 to R 18 Each independently is a mercapto group, a monovalent hydrocarbon group comprising a mercapto group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a combination thereof; however,
R 17 and R 18 Is a mercapto group or a monovalent hydrocarbon group containing a mercapto group, and p is an integer in the range of 0 to 100, and q is an integer in the range of 2 to 100.
2. The dual curable resin composition according to claim 1, wherein R in chemical formula 3 9 To R 14 Each independently substituted or unsubstituted C1 to C10 alkyl.
3. The dual curable resin composition according to claim 1, wherein the first polyorganosiloxane is represented by the following chemical formula 2:
wherein, in chemical formula 2,
R 1 to R 8 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 aralkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C1 to C20 heterocycloalkyl group, a substituted or unsubstituted C1 to C20 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a combination thereof; however,
R 1 to R 6 Is a substituted or unsubstituted C2 to C20 alkenyl group, and
R 1 to R 6 Is a substituted or unsubstituted C1 to C20 alkoxy group,
n is an integer in the range of 50 to 1000.
4. The dual curable resin composition according to claim 3, wherein R in chemical formula 2 1 To R 6 Is a substituted or unsubstituted C2 to C10 alkenyl group, and R 1 To R 6 Is a substituted or unsubstituted C1 to C10 alkoxy group.
5. The dual curable resin composition according to claim 1, wherein R in chemical formula 3 15 And R 16 Each independently is a substituted or unsubstituted C1 to C20 alkyl group, and R 17 Or R 18 Is a monovalent hydrocarbon group containing a mercapto group.
6. The dual curable resin composition according to claim 5, wherein R in chemical formula 3 9 To R 14 Each independently substituted or unsubstituted C1 to C10 alkyl.
7. The dual curable resin composition according to any one of claims 1 to 6, wherein R in chemical formula 1 x Is a substituted or unsubstituted C1 to C4 alkyl group, and X is a C1 to C6 alkoxy group.
8. The dual curable resin composition according to any one of claims 1 to 6, wherein (D) the photopolymerization initiator comprises at least one of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate.
9. The dual curable resin composition according to any one of claims 1 to 6, wherein (E) the condensation reaction catalyst comprises at least one of titanium tetra (isopropoxide), titanium tetra (n-butoxide), titanium tetra (t-butoxide), titanium di (isopropoxide) bis (ethylacetoacetate) and titanium di (isopropoxide) bis (methylacetoacetate), titanium di (isopropoxide) bis (acetylacetonate).
10. The dual curable resin composition according to any one of claims 1 to 6, comprising:
1 to 20 parts by weight of (B) a second polyorganosiloxane relative to 100 parts by weight of (a) the first polyorganosiloxane;
0.5 to 20 parts by weight of (C) the silane compound or a partially hydrolyzed compound thereof;
0.05 to 2 parts by weight of (D) the photoinitiator; and
0.05 to 10 parts by weight of (E) the condensation reaction catalyst.
11. The dual curable resin composition according to any one of claims 1 to 6, further comprising (F) an additive comprising at least one of a reinforcing filler, a photopolymerization inhibitor and a pigment.
12. A cured body prepared by curing a dual curable resin composition, wherein the dual curable resin composition is the dual curable resin composition of any one of claims 1 to 11.
13. An electronic device comprising the cured body of claim 12.
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| KR1020170097097A KR20190013091A (en) | 2017-07-31 | 2017-07-31 | Dually-Curable Resin Composition, Cured Body Prepared Therefrom, And Electronic Device Comprising Such Cured Body |
| PCT/US2018/044586 WO2019028013A1 (en) | 2017-07-31 | 2018-07-31 | Dually-curable resin composition, cured body prepared therefrom, and electronic device comprising such cured body |
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| KR20190013091A (en) | 2017-07-31 | 2019-02-11 | 다우 실리콘즈 코포레이션 | Dually-Curable Resin Composition, Cured Body Prepared Therefrom, And Electronic Device Comprising Such Cured Body |
| TWI831823B (en) | 2018-10-08 | 2024-02-11 | 美商陶氏有機矽公司 | Dual curable organopolysiloxane composition |
| TW202118833A (en) | 2019-11-13 | 2021-05-16 | 美商陶氏有機矽公司 | Room temperature storage-stable uv/vis and moisture dual curable polysiloxane composition |
| US20230167246A1 (en) | 2020-04-14 | 2023-06-01 | Wacker Chemie Ag | Polysiloxanes with radiation- and moisture-cross-linkable groups |
| TW202210558A (en) * | 2020-09-01 | 2022-03-16 | 美商陶氏全球科技公司 | Uv/moisture dual cure composition with enhanced substrate adhesion |
| KR102613806B1 (en) * | 2021-07-02 | 2023-12-15 | 주식회사 케이비지 | UV moisture hybrid curable polysiloxane composition, polysiloxane cured film prepared therefrom, and uses thereof |
| KR102595290B1 (en) * | 2021-07-08 | 2023-10-30 | 주식회사 케이비지 | Silicone conformal coating composition, silicone cured film prepared therefrom, and use thereof |
| CN114316891B (en) * | 2021-12-30 | 2023-11-28 | 深圳市安品有机硅材料有限公司 | Deep-cured room-temperature vulcanized organic silica gel and preparation method thereof |
| KR102619618B1 (en) * | 2022-12-22 | 2024-01-04 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Silicone-based composition and cured product thereof |
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- 2018-07-31 KR KR1020207004100A patent/KR102657644B1/en active IP Right Grant
- 2018-07-31 WO PCT/US2018/044586 patent/WO2019028013A1/en unknown
- 2018-07-31 EP EP18755630.3A patent/EP3662019A1/en active Pending
- 2018-07-31 JP JP2020503902A patent/JP7343475B2/en active Active
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Also Published As
| Publication number | Publication date |
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| TW201910437A (en) | 2019-03-16 |
| CN110945080A (en) | 2020-03-31 |
| WO2019028013A1 (en) | 2019-02-07 |
| KR102657644B1 (en) | 2024-04-17 |
| KR20200026990A (en) | 2020-03-11 |
| US20200207985A1 (en) | 2020-07-02 |
| EP3662019A1 (en) | 2020-06-10 |
| KR20190013091A (en) | 2019-02-11 |
| US11390748B2 (en) | 2022-07-19 |
| JP2020529489A (en) | 2020-10-08 |
| JP7343475B2 (en) | 2023-09-12 |
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